Nanowire-based hydrodesulfurization catalysts for hydrocarbon fuels

ABSTRACT

The present development is a metal particle coated nanowire catalyst for use in the hydrodesulfurization of fuels and a process for the production of the catalyst. The catalyst comprises titanium(IV) oxide nanowires wherein the nanowires are produced by exposure of a TiO2—KOH paste to microwave radiation. Metal particles selected from the group consisting of molybdenum, nickel, cobalt, tungsten, or a combination thereof, are impregnated on the metal oxide nanowire surface. The metal impregnated nanowires are sulfided to produce catalytically-active metal particles on the surface of the nanowires The catalysts of the present invention are intended for use in the removal of thiophenic sulfur from liquid fuels through a hydrodesulfurization (HDS) process in a fixed bed reactor. The presence of nanowires improves the HDS activity and reduces the sintering effect, therefore, the sulfur removal efficiency increases.

DOMESTIC BENEFIT INFORMATION/PRIORITY CLAIM

The present application claims priority to U.S. Patent Application62/440,937 filed 2016 Dec. 30, and U.S. patent application Ser. No.15/859,288 filed 2017 Dec. 29, currently pending, and PCT/US18/12006filed 1 Jan. 2018, now expired, all of which are incorporated byreference in their entireties.

GOVERNMENT INTEREST

This invention was made with government support under grant numberSC0015808 awarded by the U.S. Department of Energy. The government hascertain rights in the invention.

BACKGROUND

The presently-disclosed subject matter relates to the production oftitanium dioxide (TiO₂) nanowires, catalyst compositions and methods fordesulfurization. In particular, the presently-disclosed subject matterrelates to catalyst compositions and methods for desulfurization thatmake use of titanium(IV) oxide nanowires that includecatalytically-active metal sulfide nano-particles or nanowires as anactive phase, and more particularly wherein the metal is selected fromthe group consisting of molybdenum, nickel, cobalt, tungsten and acombination thereof.

Although the motor fuels market in the US is dominated by gasoline, thedemand for diesel fuel remains strong and is growing. Comparing USdemand in June 2014 to that of June 2015, clean-diesel vehicle salesincreased by 25%, and demand for on-road diesel fuel increased by 11.8%.In contrast, demand for gasoline decreased by 3.4%. The market share fordiesel-fueled vehicles, approximately 3% of US vehicle sales now, maydouble by 2018. Unfortunately, sulfur contamination is a major problemin diesel fuels.

Sulfur is a natural component in crude oil and therefore is also presentin gasoline and diesel fuel. With respect to diesel, light cycle oil(LCO), a middle distillate product in the fluid catalytic cracking (FCC)of heavy oils, such as vacuum gas oil and atmospheric residue, isusually blended in the diesel pool. However, LCO, which comprises about15% of the total US distillate pool, is a poor diesel fuel blendingcomponent, due to its low cetane number which is typically from about 15to about 25, and its high sulfur content, which can range from about2000 ppm to about 7000 ppm. The high sulfur content means that deephydrotreatment is required to obtain sulfur-free and high-cetane-numberfuel. In addition, the presence of sulfur increases SOx emissions,contributes to the emission of fine particulates, leads to the corrosionof engine systems (which decreases engine life), and irreversiblypoisons the noble metal catalysts in the engine's converter. For all ofthese reasons, the reduction of sulfur in diesel fuel is important.

Since September 2007, all of the on-highway diesel fuel sold at gasstations in the United States is ultra-low-sulfur diesel (ULSD), forwhich the allowable sulfur content is 15 ppm. Beginning in 2017, newvehicle emission standards issued by the US EPA Tier 3 program willlower the allowable sulfur content of gasoline from 30 ppm to 10 ppm.Consequently, refineries are facing major challenges to meet this fuelsulfur specification.

Thus, in the past decade, clean fuels research, including ultra-deepdesulfurization, has become a more important subject of environmentalcatalysis studies worldwide. One aspect of this research is identifyingcatalysts that can be highly effective in the hydrodesulfurizationprocess (HDS). Related to this is identifying processes that can behighly efficient in producing catalysts for use in HDS processes.

SUMMARY OF THE PRESENT INVENTION

The present development is a process for the production of metal oxidenanowires decorated with mono- or bimetals. The metal oxide used formaking the nanowire may be titanium(IV) oxide (TiO₂), silicon oxide(SiO₂), tin oxide (SnO₂), alumina, or a combination thereof, and themetals for decorating the nanowires may be selected from molybdenum,nickel, cobalt, tungsten and combinations thereof. In a preferredembodiment, the present development is a process for the production oftitanium(IV) oxide nanowires and/or porous titanium(IV) oxide nanowiresdecorated with mono- or bimetals selected from the group consisting ofmolybdenum, nickel, cobalt, tungsten, and a combination thereof.

The process comprises the following steps: (a) preparing a paste from ametal oxide powder and a hydroxide salt and water, (b) spreading thepaste as a thin layer on a substrate, (c) exposing the paste-coatedsubstrate to microwave radiation to form a metal oxide nanowire, and (d)loading one or more catalytically-active metals onto the metal oxidenanowire via impregnation or incipient wetness techniques.

The present development is further a process for using the metal oxidenanowires decorated with mono- or bimetals in a hydrodesulfurizationprocess. The process involves providing a metal oxide nanowire decoratedwith mono- or bimetals and exposing the decorated metal oxide nanowireto a sulfiding agent to produce a metal oxide nanowire withcatalytically-active metal sulfide particles on the surface, and thenusing the sulfided nanowire to remove sulfur-containing compounds fromhydrocarbon feedstocks. Specifically, the catalysts of the presentinvention are intended use in the removal of thiophenic sulfur fromliquid fuels through a hydrodesulfurization (HDS) process in a fixed bedreactor. The presence of nanowires improves the HDS activity and reducesthe sintering effect, therefore, the sulfur removal efficiencyincreases.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1a is a schematic of a microwave conveyor belt system used formicrowave exposure assisted nanowires production;

FIG. 1b is a photograph of a TiO₂ and KOH mixed paste spread on analumina substrate prior to microwave exposure;

FIG. 1c is a scanning electron microscopy (SEM) image of theas-synthesized TiO₂ nanowires;

FIG. 2 is an SEM image of fresh TiO₂ nanowires;

FIG. 3 is an SEM image of fresh Ni and Mo loaded on TiO₂ nanowires atlow magnification (mag=2,559×);

FIG. 4 is an SEM image of fresh Ni and Mo loaded on TiO₂ nanowires athigh magnification (mag=23,665×);

FIG. 5 is schematic drawing of fresh Ni and Mo loaded on TiO₂ nanowiresfollowed by exposure of the catalyst to a sulfiding agent to produce asulfide;

FIG. 6 is a graph of HDS activities of the 3% NiO-12% MoO₃-65% TiO₂-20%γ-Al₂O₃ catalyst from Example 7 and the Topsoe BRIM™ TK561 catalyst fromExample 8;

FIG. 7 is an SEM image of spent Ni and Mo loaded on TiO₂ nanowires atlow magnification (mag=2,691×);

FIG. 8 is an SEM image of spent Ni and Mo loaded on TiO₂ nanowires athigh magnification (mag=26,430×);

FIG. 9 is a graph showing the XRD pattern of fresh and spent Ni and Moloaded on TiO₂ nanowires; and,

FIG. 10 is a graph of a comparison of the total sulfur concentrationswith and without the H₂S removal process.

DETAILED DESCRIPTION OF THE INVENTION

The present development is a process for the production of a catalystcomprising a metal oxide nanowire with catalytically-active metalsulfide particles on the surface. More specifically, the presentinvention is a process for the production of a catalyst comprising metaloxide nanowires as a support impregnated with decorating metals that areexposed to a sulfiding agent to produce a metal oxide nanowire withcatalytically-active metal sulfide particles on the surface. The metaloxide for making the metal oxide nanowire may be titanium(IV) oxide(TiO₂), silicon oxide (SiO₂), tin oxide (SnO₂), γ-alumina, or acombination thereof, and the metals for impregnating or decorating thenanowires may be selected from molybdenum, nickel, cobalt, tungsten andcombinations thereof. In a preferred embodiment, the present developmentis a process for the production of titanium(IV) oxide nanowires and/orporous titanium(IV) oxide nanowires decorated with mono- or bimetalsselected from the group consisting of molybdenum, nickel, cobalt,tungsten, and a combination thereof. The resulting catalyst may be usedin the hydrodesulfurization process in oil refining processes.

The process of the present invention improves on the methods of theprior art by being significantly faster for the formation of the metaloxide nanowires than the prior art, thereby allowing for increasedproduction in a predetermined time period. For example, the presentinvention can produce metal oxide nanowires from a paste comprising ametal oxide powder, with or without a binder, and a hydroxide salt inless than about one minute as compared to the prior art processes thatcan take several hours. The present method is accomplished by causingthe nanowires to form by exposure to microwave radiation. Specifically,metal oxide nanowires are prepared according to the present invention bymixing a metal oxide powder (MO) and a hydroxide salt (MOH), such asKOH, with sufficient water to form a paste. The MO-MOH paste is spreadon an inert substrate as a thin film. The film-covered substrate isexposed to microwave energy for less than one minute and the product iscollected. In a preferred embodiment, the film-covered substrate isexposed to microwave energy on a moving conveyor belt. The resultingproduct is a mass of metal oxide nanowires having a length of from about0.1 μm to about 10 μm. A schematic of the process is shown in FIG. 1 a.

Generally, the process of the present invention is a multistep processthat comprises: (a) preparing a paste from a metal oxide powder, with orwithout a binder, and a hydroxide salt and water; (b) spreading thepaste as a thin film on a substrate; (c) exposing the paste-coatedsubstrate to microwave radiation to form a metal oxide nanowire; (d)loading one or more decorating metals onto the metal oxide nanowire; and(e) exposing the metal impregnated metal oxide nanowire to a sulfidingagent to produce a metal oxide nanowire with catalytically-active metalsulfide particles on the surface. The nanowire morphology and conversioncan be increased by reducing the paste film thickness on the substrate,or by increasing the film uniformity by better metal precursor andalkali salt mixing, or by optimizing the precursor ratio, or byincreasing the microwave power, or by preventing non-uniform heating, orby a combination thereof.

FIG. 1b is a photograph of a titanium(IV) oxide (TiO₂) and potassiumhydroxide (KOH) mixed paste spread on an alumina substrate prior tomicrowave exposure as per step (b) of the process. FIG. 1c is a scanningelectron microscopy (SEM) image of the as-synthesized TiO₂ nanowiresfollowing step (c) of the process.

It is anticipated that the metal oxide used for making the nanowire maybe titanium(IV) oxide (TiO₂), silicon oxide (SiO₂), tin oxide (SnO₂),alumina, or a combination thereof. Optionally, as is known in the art, abinder, such as alumina, bentonite clay or combinations thereof, may beadded to the paste to improve crushing strength. In a preferredembodiment, the nanowire is a TiO₂ nanowire or a TiO₂/Al₂O₃ nanowire. Inthe TiO₂/Al₂O₃ nanowire, the Al₂O₃ preferably comprises from 0 wt % toabout 25 wt % of the nanowire and more preferably comprises from about 5wt % to about 20 wt % of the nanowire. Further, as is known in the art,nanowire lengths and diameters will vary. In a preferred embodiment ofthe present invention, the nanowires have a length of from about 100 nmto about 10 μm and a diameter of from about 5 nm to about 50 nm. TheTiO₂ nanowires further preferably have an average surface area of about25 m² per gram of nanowires.

Exemplary metals for decorating the nanowires include molybdenum,nickel, cobalt, tungsten, their respective oxides, alloys of two or moreof these metals, and combinations thereof. The decorating metals may bein the form of an elemental metal or an oxide. It is recommended thatthe decorating metals be loaded onto the metal oxide nanowire using wetimpregnation or incipient wetness techniques, although other methodsknown in the art may be used. If wet impregnation or incipient wetnesstechniques are used, the metals are preferably provided as metalnitrates or metal acetates, as is known in the art, although othersources for the decorating metals are not precluded. By following theprocess of the present invention, the decorating metals are deposited onthe surface of the nanowires as particles. Without limiting the scope ofthe invention, it is recommended that the diameter of the decoratingmetal particles be from about 2 nm to about 20 nm. Further, as is knownin the art, following impregnation of the nanowire with the metalparticles, the metal impregnated nanowire may be thermally treated.Exemplary means for thermally treating the metal impregnated nanowiresinclude microwave radiation or a thermal furnace. Representativeexamples of decorating metals on a nanowire support include, but are notlimited to, nickel and molybdenum on titanium(IV) oxide nanowires(NiMo/TiO₂ or the oxide Ni_(x)Mo_(1-x)O₃/TiO₂), cobalt and molybdenum ontitanium(IV) oxide nanowires (CoMo/TiO₂ or the oxideCo_(x)Mo_(1-x)O₃/TiO₂), nickel and cobalt and molybdenum on titanium(IV)oxide nanowires (NiCoMo/TiO₂), nickel and molybdenum on titanium(IV)oxide and silicon oxide nanowires (NiMo/TiO₂—SiO₂), cobalt andmolybdenum on titanium(IV) oxide and silicon oxide nanowires(CoMo/TiO₂—SiO₂), nickel and cobalt and molybdenum on titanium(IV) oxideand silicon oxide nanowires (Ni—Co—Mo/TiO₂—SiO₂), nickel and molybdenumon titanium(IV) oxide nanowires with alumina (NiMo/TiO₂—Al₂O₃), cobaltand molybdenum on titanium(IV) oxide nanowires with nanowires(CoMo/TiO₂—Al₂O₃), nickel and cobalt and molybdenum on titanium(IV)oxide nanowires with alumina (Ni—Co—Mo/TiO₂—Al₂O₃).

The decorating metal loading is preferably from about 3 wt % to about 20wt %, and is more preferably from about 3 wt % to about 15 wt %.Further, the loading may be metal dependent. For example, nickel orcobalt or nickel-cobalt loading preferably ranges from about 3 wt % toabout 15 wt %, and more preferably from about 3 wt % to about 10 wt %,whereas molybdenum loading preferably ranges from about 10 wt % to about20 wt %, and more preferably from about 12 wt % to about 18 wt %.

As indicated supra, the process of the present invention is a multistepprocess. In an exemplary embodiment for the preparation of the decoratedmetal oxide nanowires (steps a-d), (a) TiO₂ and KOH powders are mixed inan approximately 5:1 weight ratio (TiO₂:KOH) and made into paste form byadding water; (b) the TiO₂—KOH paste is spread on an alumina substrateas a thin film with thickness of approximately 0.25 inches; (c) thealumina substrate with the TiO₂—KOH paste material is exposed tomicrowave energy of about 915 MHz, 10 kW for about 45 seconds in amoving conveyor belt facility to produce TiO₂ nanowires; and (d) thedecorating metal nickel is loaded onto the TiO₂ nanowires using wetimpregnation techniques such that the final metal loading is preferablyfrom about 3 wt % to about 15 wt %. As shown in the SEM images of FIG.2, the as-synthesized product after step (c) is a mass of TiO₂ nanowireshaving a length of from about 5 μm to about 10 μm. Wet impregnationtechniques, as used in step (d) are known in the art. In the presentexemplary embodiment, it is recommended that an aqueous solution ofnickel nitrates or nickel acetates be used for loading the decoratingmetals onto the nanowires.

As is known in the art, the metal coated nanowires may be dried andshaped into extrudates and calcination in a furnace at a predeterminedtemperature for a predetermined period of time. The catalyst propertiesmay be characterized by X-ray diffraction (XRD), scanning electronmicroscopy (SEM), transition electron microscopy (TEM), X-rayphotoelectron spectroscopy (XPS), and other techniques known in the art.In a preferred embodiment, the metal coated nanowires are dried andshaped into extrudates of about 1.2 mm diameter and about 1 cm lengthand are calcined at from about 400° C. to about 500° C. for from about 2hours to about 4 hours. An SEM image of a NiMo/TiO₂ nanowire catalyst assynthesized is shown in FIGS. 3 and 4.

The decorated metal oxide nanowires are intended to be used in thehydrodesulfurization process in the oil refining processes. Prior tousing the catalyst for hydrodesulfurization, it is beneficial to subjectthe catalyst to an activation or sulfidation step. Without limiting thescope of the invention, it is recommended that sulfidation be carriedout by treating the decorated metal oxide nanowires either with hydrogensulfide or with dimethyl disulfide. Exposing the decorated metal oxidenanowire or metal impregnated metal oxide nanowire to a sulfiding agentproduces a metal oxide nanowire with catalytically-active metal sulfideparticles on the surface. FIG. 5 is a schematic of the sulfidationprocess. The metal oxide nanowire with catalytically-active metalsulfide particles may be used to remove an assortment of refractorysulfur species, such as thiophene, benzothiophene (BT), dibenzothiophene(DBT), 4,6-dimethyldibenzothiophene (DMDBT), 4-methyldibenzothiophene(MDBT) or a combination thereof, in the hydrodesulfurization ofhydrocarbon fuels selected from the group consisting light cycle oil(LCO), diesel fuel, jet fuel, kerosene, similar sulfur containinghydrocarbons, and combinations thereof. Further, the presence ofnanowires improves the HDS activity and reduces the sintering effect,therefore, the sulfur removal efficiency increases. When the metal oxidenanowire with catalytically-active metal sulfide particles is a titaniumoxide-alumina nanowire, the sulfur content may be reduced to aconcentration of about 20 ppm more effectively and efficiently than theprior art commercial catalyst.

The following examples are intended to provide the reader with a betterunderstanding of the invention. The examples are not intended to belimiting with respect to any element not otherwise limited within theclaims. For example, the present invention will be described in thecontext of titanium(IV) oxide nanowires, but the teachings herein arenot limited to titanium(IV) oxide nanowires.

Catalyst Preparation

TiO₂ Nanowire Synthesis—Present Invention:

Titanium(IV) oxide nanowires are prepared according to the presentinvention by mixing TiO₂ powder and KOH powder in an approximately 5:1weight ratio (TiO₂:KOH) and made into paste form by adding water. TheTiO₂—KOH paste is spread on a γ-alumina substrate as a thin film havinga thickness of approximately 0.25 inches. The film-covered substrate isexposed to microwave energy of 915 MHz, 10 kW for about 45 seconds in amoving conveyor belt facility. As shown in the SEM images of FIG. 2, theas-synthesized product is a mass of TiO₂ nanowires having a length offrom about 5 μm to about 10 μm.

TiO₂ Nanowire Synthesis—Prior Art Method:

Titanium(IV) oxide nanowires and porous titanium(IV) oxide nanowires areprepared by mixing TiO₂ powder and KOH powder in an approximately 5:1weight ratio (TiO₂:KOH) and then placing the powder mixture in a furnaceat temperatures of from about 800° C. to about 1000° C. for time periodof from about 1 hour to about 4 hours to form K₂TiO₃ powder. The K₂TiO₃powder is removed from the furnace and washed with 0.5 M HCl acid forabout 15 minutes to 30 minutes. The washed powder is filtered and thenwashed with deionized (DI) water. The DI-washed powder is then dried inan oven at temperatures of from about 80° C. to about 120° C. for fromabout 1 hour to about 3 hours. After the oven drying, the oventemperature is raised at a rate of about 5° C. per minute to atemperature of about 450° C. and the material is calcined at about 450°C. for about 3 hours to obtain TiO₂ nanowires and porous TiO₂ nanowires.

NiCoMo/TiO₂ Catalyst:

A 20 g sample of a NiCoMo/TiO₂ catalyst having the composition 3% NiO-3%Co₃O₄-15% MoO₃-79% TiO₂ is prepared. A mixture solution containing about2.336 g nickel nitrate hexahydrate, about 3.679 g ammoniumheptamolybdate and about 2.175 g cobalt nitrate hexahydrate dissolved inabout 15 ml of DI H₂O is prepared at a temperature of about 23° C. withgentle stirring. Approximately 15.8 g TiO₂ nanowires prepared accordingto the present invention are added to the metal solution mixture and themetals are co-impregnated onto the nanowires by stirring for about 20minutes and then removing the metal-treated nanowires from the solutionand spreading them onto a tray and then drying them in an oven set atabout 120° C. for approximately 15 hours. After the oven drying, andwithout removing the metal-treated nanowires from the oven, the oventemperature is raised at a rate of about 5° C. per minute to atemperature of about 450° C. and the metal-treated nanowires arecalcined at about 450° C. for about 3 hours to produce anickel/cobalt/molybdenum decorated titanium oxide nanowire catalysthaving the composition 3% NiO-3% Co₃O₄-15% MoO₃-79% TiO₂.

NiMo/TiO₂—Al₂O₃Catalyst:

A 20 g sample of a NiMo/TiO₂—Al₂O₃ catalyst having the composition 3%NiO-12% MoO₃-65% TiO₂-20% Al₂O₃ is prepared. A mixture solutioncontaining about 2.336 g nickel nitrate hexahydrate and about 2.944 gammonium heptamolybdate is dissolved in about 20 ml of DI water isprepared at a temperature of about 23° C. with gentle stirring.Approximately 13 g TiO₂ nanowires prepared according to the presentinvention and 4 g γ-Al₂O₃ powder are added to the metal solution mixtureand the metals are co-impregnated onto the nanowires by stirring forabout 20 minutes and then removing the treated nanowires from thesolution and spreading them onto a tray and then drying them in an ovenset at about 120° C. for approximately 15 hours. After the oven drying,and without removing the metal-treated nanowires from the oven, the oventemperature is raised at a rate of about 5° C. per minute to atemperature of about 450° C. and the treated nanowires are calcined atabout 450° C. for about 3 hours to produce a nickel/molybdenum decoratedtitanium oxide and alumina nanowire catalyst having the composition 3%NiO-12% MoO₃-65% TiO₂-20% Al₂O₃.

CoMo/TiO₂—Al₂O₃ Catalyst:

A 20 g sample of a cobalt/molybdenum decorated titanium oxide andalumina nanowire (CoMo/TiO₂—Al₂O₃) catalyst having the composition 3%Co₃O₄-12% MoO₃-65% TiO₂-20% Al₂O₃ catalyst is prepared. The preparationmethod is identical to the method for preparation of the NiMo/TiO₂—Al₂O₃catalyst except 2.175 g cobalt nitrate hexahydrate solution is used inplace of the 2.336 g nickel nitrate hexahydrate solution.

Hydrodesulfurization Process

Sulfidation:

Prior to using the catalyst for hydrodesulfurization, it is beneficialto subject the catalyst to an activation or sulfidation step. Freshlyprepared decorated metal oxide nanowires are packed into a stainlesssteel fixed bed reactor. Although not required for the catalyst tofunction, it is recommended that prior to loading the reactor bed, thecatalyst be crushed to particles with dimensions of about 1.2 mm toabout 1.5 mm diameter and a length of 3 mm to about 5 mm to improvecontact of the hydrocarbon feedstock that is to be subjected tohydrodesulfurization process. The packed catalyst is then pretreated byheating the reactor to a temperature of about 150° C. and flowingnitrogen gas (N₂) over the catalyst bed for about 2 hours. The catalystis then subjected to the sulfidation step. Without intending to limitthe scope of the inventions, the following two methods for sulfidationare suggested:

Sulfidation with H₂S:

10 vol % H₂S in H₂ gas is allowed to flow over the packed catalyst at atemperature of about 400° C. for from about 4 hours to about 15 hours.The H₂S flow time will vary depending on the catalyst metal loading.

Sulfidation with DMDS:

Diesel feedstock is allowed to flow over the packed catalyst at atemperature of about 120° C. for from approximately 2 hours toapproximately 4 hours to ensure complete catalyst wetting. The reactortemperature is increased to temperatures from about 200° C. to about240° C. and then dimethyl disulfide liquid (DMDS) is injected onto thecatalyst along with the diesel feedstock at a concentration to maintainfrom about 1 wt % to about 2 wt % sulfur concentration. Thefeedstock/DMDS flow is continued until sulfur breakthrough is observedat from about 3000 ppm to about 3500 ppm sulfur in the outlet ofreactor. The reactor temperature is then raised to about 340° C. at arate of from about 10° C./hr to about 15° C./hr and the temperature ismaintained to about 340° C. for from about 1 hour to about 2 hours. Theflow of DMDS onto the catalyst is then stopped.

Hydrodesulfurization:

The hydrodesulfurization testing is conducted using a model hydrocarbonstream spiked with from about 400 ppm to about 700 ppm sulfur by weightwith an assortment of refractory sulfur species to closely resembleindustrial conditions. Decorated metal oxide nanowires are loaded into afixed bed reactor and sulfided. Following sulfidation, the reactortemperature is cooled to a hydrodesulfurization temperature of fromabout 300° C. to 400° C., and more preferably at from about 350° C. to375° C. A hydrogen flow is started to pressurize the reactor to an HDSpressure of from about 15 bar to about 50 bar, more preferably fromabout 20 bar to about 30 bar. A hydrocarbon feedstock is then passedthrough the catalyst at a liquid hourly space velocity of from about 0.5h⁻¹ to 3 h⁻¹, more preferably at about 1 h⁻¹.

Hydrodesulfurization of LCO using NiMo/TiO₂—Al₂O₃ Catalyst:

About 20 g of a NiMo/TiO₂—Al₂O₃ catalyst (3% NiO-12% MoO₃-65% TiO₂-20%γ-Al₂O₃) is diluted with about 35 g of SiC and packed into the fixed bedreactor as three beds of approximately 18 g each interlayered betweenlayers of glass beads. The catalyst is pretreated at a temperature ofabout 150° C. with N₂ for about 2 hours. The catalyst is then sulfidedwith 10 vol % H₂S in H₂ gas at a temperature of about 400° C. for fromabout 6 hours. The reactor is cooled to a temperature of about 350° C.to about 380° C. and is pressurized to a pressure of about 15 bar toabout 30 bar. A light cycle oil (LCO) hydrocarbon feed obtained from anoil refinery and having about 600 ppm to about 740 ppm by weight ofsulfur is then passed through the catalyst at a liquid hourly spacevelocity of 0.5 h⁻¹ to 2 h⁻¹. As the gas exits the reactor, the H₂S andunreacted H₂ gases are separated by a gas-liquid separator and exited toa vent, and the HDS treated liquid fuel exits from the reactor and isstored in a product tank. The total sulfur concentration was analyzedusing UV-Fluorescence (ASTM D5453). The HDS activity of the 3% NiO-12%MoO₃-65% TiO₂-20% γ-Al₂O₃ catalyst is shown in Table 1.

TABLE 1 HDS of LCO samples from a small oil refinery Time on Sulfurconcentration stream LHSV Temperature Pressure at outlet (h) (h⁻¹) (°C.) (bar) (ppm)  0-50 1 350 15 55 ± 10  51-100 0.5 350 15 45 ± 10101-150 0.5 380 15 40 ± 10 151-350 0.5 380 20 20 ± 10 351-400 1 380 3035 ± 10

Hydrodesulfurization of diesel fuel using NiMo/TiO₂—Al₂O₃ Catalyst:

About 20 g of fresh NiMo/TiO₂—Al₂O₃ catalyst (3% NiO-12% MoO₃-65%TiO₂-20% γ-Al₂O₃) is diluted with about 35 g of SiC and packed into thefixed bed reactor as three beds of approximately 18 g each interlayeredbetween layers of glass beads. The catalyst is pretreated at atemperature of about 150° C. with N₂ for about 2 hours. The catalyst isthen sulfided with 10 vol % H₂S in H₂ gas at a temperature of about 430°C. for from about 6 hours. The reactor is cooled to a temperature ofabout 350° C. and is pressurized to a pressure of about 20 bar to about30 bar. A diesel feed obtained from a local gas station spiked to about400 ppm by weight sulfur with 90% thiophene and 10% a combination ofbenzothiophene (BT), dibenzothiophene (DBT),4,6-dimethyldibenzothiophene (DMDBT), and 4-methyldibenzothiophene(MDBT) is then passed through the catalyst at a liquid hourly spacevelocity of 0.5 h⁻¹ to 2 h⁻¹. As the gas exits the reactor, the H₂S andunreacted H₂ gases are separated by a gas-liquid separator and exited toa vent, and the HDS treated liquid fuel exits from the reactor and isstored in a product tank. The total sulfur concentration was analyzedusing UV-Fluorescence (ASTM D5453). For comparison, the reaction isrepeated using the same conditions and hydrocarbon feed except 20 g ofTopsoe BRIM™ TK561 catalyst are used in place of the NiMo/TiO₂—Al₂O₃catalyst. The total sulfur concentration was analyzed usingUV-Fluorescence. The HDS activity of the 3% NiO-12% MoO₃-65% TiO₂-20%γ-Al₂O₃ catalyst and the Topsoe BRIM™ TK561 catalyst are reported inTable 2 and shown in the graph at FIG. 6. The catalyst of the presentinvention removes sulfur more effectively and to a lower concentrationthan the prior art commercial catalyst.

TABLE 2 HDS of Sulfur spiked diesel samples using two catalyst samplesTiO₂ NW Topsoe based catalyst BRIM ™ TK561 Time on Sulfur conc. Sulfurconc stream LHSV Temp Pressure at outlet Pressure at outlet (h) (h⁻¹) (°C.) (bar) (ppm) (bar) (ppm) 20 1 350 20 90 30 160 40 1 350 20 25 30 12050 1 350 20 17 30 40 75 1 350 20 25 30 30 100 1 350 20 20 30 35

Catalyst Integrity:

The spent NiMo/TiO₂—Al₂O₃ catalyst from the hydrodesulfurization of LCOexperiment was examined using scanning electron microscopy (SEM). Acomparison of the SEM images of the spent catalyst, shown in FIGS. 7 and8, as compared to the fresh as-synthesized catalyst, shown in FIGS. 3and 4, indicates that the catalyst maintained its morphology even duringthe HDS process. As shown in FIG. 8, the NiMoS nanoparticles were stilluniformly present on the surface of the nanowire. FIG. 9 shows the X-raydiffraction patterns of the fresh and spent NiMo/TiO₂ nanowires catalystsamples. The peaks of Mo₂S confirmed that sulfidation occurred.

We have observed that the H₂S gas generated from the HDS reactiondissolves into liquid-phase fuel. Without being bound by theory, webelieve that this results in an increase of the total sulfur level inthe liquid product samples. In order to remove the H₂S gas moleculesfrom the liquid phase samples, N₂ flushing treatment is recommended. Arecommended flushing treatment uses a high purity N₂ gas that is flowedthrough the collected HDS fuel sample from the product tank for a periodof about 2 hours. A comparison of the total sulfur concentrations withand without H₂S removal process is shown in FIG. 10.

The metal oxide nanowires with the catalytically-active sulfide metalparticles of the present invention, and particularly the titanium(IV)oxide nanowires with the catalytically-active sulfide metal particles,are intended to be used in the hydrodesulfurization process in the oilrefining processes. These nanowires are unique for this purpose becausenanowire-structured catalysts have not been used for hydrotreating inoil refineries. The use of nanowire-structured catalysts is expected toresult in improved mass-transfer and an improved mechanical behaviorduring high temperature operation. Further, these nanowires are expectedto offer rapid reaction rates that overcome the diffusion limitations ofconventional pellet-based catalysts and allow all of the material to beused efficiently. It is anticipated that the catalysts of the presentinvention may be used in the hydrodesulfurization of hydrocarbon fuelsselected from the group consisting of light cycle oil, diesel, jet fuel,kerosene, and combinations thereof.

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which the presently disclosed subject matter pertains.Representative methods, devices, and materials are described herein, butare not intended to be limiting unless so noted.

The terms “a”, “an”, and “the” refer to “one or more” when used in thesubject specification, including the claims. The term “ambienttemperature” as used herein refers to an environmental temperature offrom about 0° F. to about 120° F., inclusive.

Unless otherwise indicated, all numbers expressing quantities ofcomponents, conditions, and otherwise used in the specification andclaims are to be understood as being modified in all instances by theterm “about”. Accordingly, unless indicated to the contrary, thenumerical parameters set forth in the instant specification and attachedclaims are approximations that can vary depending upon the desiredproperties sought to be obtained by the presently disclosed subjectmatter.

As used herein, the term “about”, when referring to a value or to anamount of mass, weight, time, volume, concentration, or percentage canencompass variations of, in some embodiments ±20%, in some embodiments±10%, in some embodiments ±5%, in some embodiments ±1%, in someembodiments ±0.5%, and in some embodiments to ±0.1%, from the specifiedamount, as such variations are appropriate in the disclosed application.

All compositional percentages used herein are presented on a “by weight”basis, unless designated otherwise. Specific compositions relevant tothe titanium(IV) oxide nanowires with catalytically-active metal sulfideparticles composition are provided herein for the purpose ofdemonstrating the invention, but these compositions are not intended tolimit the scope of the invention. It is understood that one skilled inthe art may make alterations to the embodiments shown and describedherein without departing from the scope of the invention.

What is claimed is:
 1. A method for hydrodesulfurization of hydrocarbonfuels the method comprising: (a) providing a fresh decorated metal oxidenanowire catalyst comprising a metal oxide nanowire loaded with one ormore decorating metals; (b) packing the fresh catalyst into a reactor;(c) sulfiding the catalyst; (d) passing a hydrocarbon feedstock throughthe catalyst to remove sulfur from the feedstock; and, (e) collectingthe desulfurized feedstock, wherein the catalyst sulfiding step (c)comprises allowing diesel feedstock to flow over the packed catalyst ata temperature of about 120° C. for from about 2 hours to about 4 hours,and then increasing the reactor temperature to temperatures from about200° C. to about 240° C. and then injecting dimethyl disulfide liquid(DMDS) onto the catalyst along with the diesel feedstock at aconcentration to maintain from about 1 wt % to about 3 wt % sulfurconcentration, and then continuing the feedstock/DMDS flow until sulfurbreakthrough is observed at from about 3000 ppm to about 3500 ppm sulfurin the outlet of reactor, and then raising the reactor temperature toabout 340° C. at a rate of from about 10° C./hr to about 15° C./hr, andthen maintaining the temperature at about 340° C. for from about 1 hourto about 8 hours, and then stopping the flow of DMDS contained sulfidingfeedstock onto the catalyst.
 2. The method of claim 1 wherein thecatalyst comprises titanium(IV) oxide nanowires, porous titanium(IV)oxide (anatase phase) nanowires, silicon oxide nanowires, tin oxidenanowires, alumina nanowires, or a combination thereof.
 3. The method ofclaim 1 wherein the decorating metal comprises molybdenum, nickel,cobalt, tungsten, molybdenum oxide, nickel oxide, cobalt oxide, tungstenoxide, or a combination thereof, or an alloy of a combination thereof.4. The method of claim 1 wherein the hydrocarbon feedstock is selectedfrom light cycle oil (LCO), light gas oil (LGO, vacuum gas oil (VGO),diesel fuel, jet fuel, kerosene, bunker fuel, extra-heavy oils, orcombinations thereof.
 5. The method of claim 1 wherein the sulfur in thefeedstock is thiophene, benzothiophene (BT), dibenzothiophene (DBT),4,6-dimethyldibenzothiophene (DMDBT), 4-methyldibenzothiophene (MDBT),or combinations thereof.
 6. The method of claim 1 wherein step (c) isachieved using a sulfiding agent and the sulfiding agent is hydrogensulfide or dimethyl disulfide.
 7. The method of claim 1 wherein thecatalyst sulfiding step comprises allowing 10 vol % H₂S in H₂ gas toflow over the packed catalyst at a temperature of about 400° C. for fromabout 4 hours to about 15 hours.
 8. The method of claim 1 wherein thefresh decorated metal oxide nanowire catalyst is formed into extrudateform with dimensions of about 1.2 mm to about 1.5 mm diameter and alength of 3 mm to about 5 mm prior to packing in the reactor.
 9. Themethod of claim 1 further including a step to pretreat the packedcatalyst by heating the reactor to a temperature of about 150° C. andflowing nitrogen gas (N₂) over the catalyst bed for about 2 hours priorto the catalyst sulfiding step (c).
 10. The method of claim 1 whereinthe temperature of the reactor is adjusted to 300° C. to 400° C. aftersulfiding the catalyst and before passing a hydrocarbon feedstockthrough the catalyst to remove sulfur from the feedstock.
 11. The methodof claim 10 wherein the temperature of the reactor is adjusted to 350°C. to 375° C.
 12. The method of claim 1 wherein the pressure of thereactor is adjusted to from about 10 bar to about 50 bar after sulfidingthe catalyst and before passing a hydrocarbon feedstock through thecatalyst to remove sulfur from the feedstock.
 13. The method of claim 12wherein the reactor is pressurized with hydrogen gas to a pressure offrom about 20 bar to about 30 bar.
 14. The method of claim 1 wherein thehydrocarbon feedstock passes through the catalyst at a liquid hourlyspace velocity of 0.5 h⁻¹ to 3 h⁻¹ to remove sulfur from the feedstock.15. The method of claim 1 wherein nitrogen gas is allowed to flowthrough the desulfurized feedstock for a predetermined period of time toremove H₂S, and the nitrogen-treated desulfurized feedstock iscollected.
 16. A method for hydrodesulfurization of hydrocarbon fuelsthe method comprising: (a) providing a fresh decorated metal oxidenanowire catalyst comprising a metal oxide nanowire loaded with one ormore decorating metals; (b) packing the fresh catalyst into a reactor;(c) sulfiding the catalyst; (d) passing a hydrocarbon feedstock throughthe catalyst to remove sulfur from the feedstock; and, (e) collectingthe desulfurized feedstock, wherein the sulfur content of thedesulfurized feedstock is less than or equal to 30 ppm sulfur.